CN104292888A - Method for preparing PVC stabilizer by taking natural ore as raw material - Google Patents
Method for preparing PVC stabilizer by taking natural ore as raw material Download PDFInfo
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- CN104292888A CN104292888A CN201410576650.0A CN201410576650A CN104292888A CN 104292888 A CN104292888 A CN 104292888A CN 201410576650 A CN201410576650 A CN 201410576650A CN 104292888 A CN104292888 A CN 104292888A
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Abstract
The invention relates to a method for preparing a PVC heat stabilizer by taking a natural ore, namely, vermiculite in Yuli County, Xinjiang (account for 95% of nationwide reserves), as a raw material. The method specifically comprises the following steps: by taking vermiculite as a raw ore, carrying out microwave expansion on the vermiculite so as to obtain expanded vermiculite; carrying out acid washing on the expanded vermiculite by using an inorganic acid so as to remove impurities, carrying out magnetic flotation on the obtained object so as to remove irons, and purifying the obtained object so as to obtain modified expanded vermiculite; and after the modified expanded vermiculite is dried, crushing the vermiculite, carrying out acid washing by using an organic acid and carrying out magnetic separation and purification, washing the obtained product by using water and drying the obtained object, so that a vermiculite PVC heat stabilizer is prepared. According to the invention, a natural ore vermiculite is selected as a raw material for preparing a PVC heat stabilizer, therefore, the method has the advantages of wide raw material sources, low cost, simple process, nontoxicity, and easiness for popularization and application; and in addition, an efficient heat stabilizer is prepared by using a raw ore vermiculite, so that a defect that existing heat stabilizers are high in price or toxic (contain lead and the like) is overcome, and a new direction is also provided for the development of high-added-value vermiculite products.
Description
Technical field
The present invention relates to the preparation method of PVC stabilizer, the special natural mineral non-toxic heat stabilizer of especially a kind of PVC.
Background technology
PVC material has high strength, cheap, and chemical resistance is good, electrical insulating property is good and the advantage such as difficult to burn, is widely used in engineering construction, food product pack, the hard of the industry such as electric and soft product.In the world, the demand of polyvinyl chloride resin occupies the 3rd after being positioned at polyethylene, polypropylene; And its consumption has risen to first at home.2010, PVC annual requirement will reach 3,700 ten thousand tons in the world, and within 2011, China PVC production capacity will reach about 2,200 ten thousand tons, be sure to occupy No. 1 in the world.
But due to the existence containing labile factors such as branch point, double bond and initiator residue in PVC polymer chain structure, the chlorosity on PVC molecular chain is easily deviate from from molecular chain, just can decompose when being heated to 140 DEG C and discharge hydrogenchloride.Along with extending heating time or temperature raise, HCl deviates from a large number and accumulates in the material, because HCl has katalysis to PVC degraded, PVC degradation speed is accelerated greatly, after deviating from HCl, in molecular chain, a large amount of formation has the conjugated double bond of adding lustre to, goods occur that color is sharply deepened, the phenomenon that physical and mechanical properties declines, and even charing is until lose use value.Therefore, when PVC product carries out forming process, thermo-stabilizer must be used.
The thirties in 20th century, first the appearance of lead salt solves the thermal degradation problems of PVC, is also the thermo-stabilizer used the earliest, but along with the enhancing of people's environmental consciousness, large, the with serious pollution problem of its toxicity significantly limit application; Created metallic soap, organotin, rare earth and a large amount of auxiliary heat stabilizers etc. afterwards gradually.
There is larger difference in the service condition of various countries' thermo-stabilizer in the world.Comparatively early, the thermo-stabilizer of its industry use is at present based on composition metal soap class, and organic tin thermo-stabilizer rate of growth is the fastest for U.S.'s PVC heat stabilizer industry starting; The development of Western European countries' PVC heat stabilizer is more late, so substantially based on the lead salt that cost performance is higher, account for 56% of market, compoundly accounts for 31%.On the whole, the larger lead salts thermo-stabilizer of toxicity is generally in negative growth trend, and compound (the especially nontoxic Ca/Zn) of nontoxic, environmental protection is all higher than its average growth rate.
At present, on market, PVC heat stabilizer principal item used has lead salt, metallic soap, organotin, antimony organic, rare earth and various auxiliary heat stabilizers etc.Of greatest concern is non-toxic plastic product additive, and its mesolite and hydrotalcite thermo-stabilizer are exactly this class.
PVC heat stabilizer research right is at present carried out in a deep going way, and new raw materials also will constantly occur, can what is more important find a kind of cheapness and nontoxic PVC heat stabilizer, will become the emphasis becoming research and development from now on.
Summary of the invention
Goal of the invention: overcome the deficiencies in the prior art, provides a kind of natural ore to be the method that PVC stabilizer prepared by raw material.Present method utilizes Xinjiang Crude vermiculite to prepare PVC heat stabilizer, feature for raw material: low in raw material price, and preparation method is simple, and stabilising effect is obvious, achieves vermiculite high value added utilization.
The present invention can be achieved through the following technical solutions:
Natural ore is the method that PVC stabilizer prepared by raw material, it is characterized in that it comprises the following steps:
The first step: raw material and process: Crude vermiculite breeze is broken, vacuum microwave expands, and obtains expanded vermiculite;
Second step: the expanded vermiculite the first step obtained adds in dilute acid soln, puts into magnetic stirring apparatus, heating, magneton stirs, magnetic force flotation, deironing, and after certain hour, solution filters, and solid obtains modified expanded vermiculite through vacuum-drying;
3rd step: the modified expanded vermiculite power obtained by second step is broken to certain order number, adds in dilute acid soln, iron removal by magnetic separation, after certain hour, solution filters, and deionized water wash is to neutral, and solid drying, obtains Crude vermiculite thermo-stabilizer;
4th step: second step and the 3rd step filter gained acid solution, through ceramic membrane filter recycle and reuse.
Further scheme of the present invention is that the Crude vermiculite breeze described in the first step is broken to 5 order ~ 100 orders, microwave power 700W ~ 2500W, and vacuum tightness is 0.01 ~ 0.15MPa, Bulking Time 10 seconds ~ 300 seconds.
Further scheme of the present invention is diluted acid described in second step is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the mass concentration of diluted acid is 1% ~ 15%; Heating temperature is 60 DEG C ~ 100 DEG C; Magneton rotating speed is 100 turns ~ 3000 turns, 10 minutes ~ 150 minutes time, and vacuum-drying temperature is 70 DEG C ~ 120 DEG C.
Further scheme of the present invention is that the modified expanded vermiculite power of the 3rd step is broken to 160 order ~ 300 orders, and diluted acid is formic acid, acetic acid, propionic acid, and mass concentration is 0.1% ~ 10%, 5 minutes ~ 120 minutes time.
The present invention is compared with art methods, present method take natural ore as raw material, adopts Xinjiang Vermiculite ore deposit to prepare PVC heat stabilizer, overcomes the limitation of existing cost height and leaded poisonous thermo-stabilizer, extend the kind of raw materials and PVC heat stabilizer, there is following obvious advantage:
1) the present invention adopts natural mineral products vermiculite to be that PVC heat stabilizer prepared by raw material, with low cost, for PVC heat stabilizer adds newcomer, realizes raw material innovation;
2) preparation technology of the present invention is simple, and stabilising effect is obvious, and at 180 DEG C, it is not aging to reach 3 hours, is easy to apply, realizes process innovation;
3) vermiculite is the moisture graded aluminosilicates of a kind of iron magnesium (Mg, Fe, Al)
8(Si, Al)
4o
10(OH)
24H
2o, vermiculite is that thermo-stabilizer prepared by raw material, and the element such as not leaded and poisonous rare earth, possesses the feature of non-toxic heat stabilizer;
4) the present invention adopts the peculiar raw ore vermiculite in Xinjiang (Xinjiang accounts for more than 95% of the whole nation) to prepare PVC heat stabilizer, overcome current vermiculite major part as heat-stable material, wall surface material, PLASTIC LAMINATED, fireproof mortar, refractory brick, lagging material, thermal baffle, soil redeposition, fodder additives, sorbent material, flocculating aids etc., the inferior position that added value is low, provides new direction for the new opplication of vermiculite in PVC field;
In a word, the present invention selects natural ore vermiculite as raw material, and preparation PVC heat stabilizer, has the advantages such as raw material sources are extensive, with low cost, technique is simple, nontoxic, be easy to apply.
Embodiment
Embodiment 1
Xinjiang Weili county vermiculite power is broken to 5 orders, under vacuum tightness is 0.05MPa and microwave power 1000W, expands, Bulking Time 50 seconds, the expanded vermiculite of obtained expansion more than 6 times.Expanded vermiculite 150 grams is put into the hydrochloric acid soln that beaker fills the mass concentration 5% of 500 milliliters, put into magneton, then beaker is put into the thermostat water bath with magnetic agitation, Heating temperature 80 DEG C, rotating speed is 1000 turns, magnetic force flotation 50 minutes, filtration washing, the vacuum-drying at 85 DEG C of modified expanded vermiculite solid, to constant weight, obtains modified expanded vermiculite.Modified expanded vermiculite power is broken to 200 orders, put into the formic acid solution that beaker fills the mass concentration 5% of 400 milliliters, put into magneton, then beaker is put into on magnetic stirring apparatus, rotating speed is 800 turns, magnetic force flotation 40 minutes, filter, deionized water wash is to neutral, and expanded vermiculite powder vacuum-drying at 90 DEG C, to constant weight, obtains vermiculite PVC heat stabilizer.Hydrochloric acid soln and formic acid solution, after vitrified pipe filters, add a small amount of acid, recycle.
By PVC powder 50 parts, PVC paste resin 50 parts, DOP 50 parts, vermiculite thermo-stabilizer 3 parts, mix, be placed on aluminium flake, in 180 DEG C of baking ovens, plastify 5min, prepare the test piece that thickness is about 0.5mm, wide 2cm.Test according to GB/T9349-2002B standard: the sample made is put into 180.DEG C thermal ageing baking oven in carry out static heat senile experiment, get once every 10min, according to GB/T 2913-1982 standard, the whiteness of test PVC test piece.Containing vermiculite thermo-stabilizer PVC test piece, can keep 3 hours 10 minutes not aging.
Embodiment 2
Xinjiang Weili county vermiculite power is broken to 10 orders, under vacuum tightness is 0.05MPa and microwave power 1200W, expands, Bulking Time 40 seconds, the expanded vermiculite of obtained expansion more than 6 times.Expanded vermiculite 150 grams is put into the sulphuric acid soln that beaker fills the mass concentration 5% of 500 milliliters, put into magneton, then beaker is put into the thermostat water bath with magnetic agitation, Heating temperature 90 DEG C, rotating speed is 1300 turns, magnetic force flotation 50 minutes, filtration washing, the vacuum-drying at 85 DEG C of modified expanded vermiculite solid, to constant weight, obtains modified expanded vermiculite.Modified expanded vermiculite power is broken to 280 orders, put into the acetic acid solution that beaker fills the mass concentration 5% of 400 milliliters, put into magneton, then beaker is put into on magnetic stirring apparatus, rotating speed is 800 turns, magnetic force flotation 40 minutes, filter, deionized water wash is to neutral, and expanded vermiculite powder vacuum-drying at 90 DEG C, to constant weight, obtains vermiculite PVC heat stabilizer.Sulphuric acid soln and acetic acid solution, after vitrified pipe filters, add a small amount of acid, recycle.
By PVC powder 50 parts, PVC paste resin 50 parts, DOP 50 parts, vermiculite thermo-stabilizer 3 parts, mix, be placed on aluminium flake, in 180 DEG C of baking ovens, plastify 5min, prepare the test piece that thickness is about 0.5mm, wide 2cm.Test according to GB/T9349-2002B standard: the thermal ageing baking oven sample made being put into 180 DEG C carries out static heat senile experiment, gets once every 10min, according to GB/T 2913-1982 standard, the whiteness of test PVC test piece.Containing vermiculite thermo-stabilizer PVC test piece, can keep 3 hours 20 minutes not aging.
Claims (4)
1. be the method that PVC stabilizer prepared by raw material by natural ore, it is characterized in that it comprises the following steps:
The first step: raw material and process: Crude vermiculite breeze is broken, vacuum microwave expands, and obtains expanded vermiculite;
Second step: the expanded vermiculite the first step obtained adds in dilute acid soln, puts into magnetic stirring apparatus, heating, magneton stirs, magnetic force flotation, deironing, and after certain hour, solution filters, and solid obtains modified expanded vermiculite through vacuum-drying;
3rd step: the modified expanded vermiculite power obtained by second step is broken to certain order number, adds in dilute acid soln, iron removal by magnetic separation, after certain hour, solution filters, and deionized water wash is to neutral, and solid drying, obtains Crude vermiculite thermo-stabilizer;
4th step: second step and the 3rd step filter gained acid solution, through ceramic membrane filter recycle and reuse.
2. a kind of natural ore according to claim 1 is the method that PVC stabilizer prepared by raw material, it is characterized in that: the Crude vermiculite breeze described in the first step is broken to 5 order ~ 100 orders, microwave power 700W ~ 2500W, vacuum tightness is 0.01 ~ 0.15MPa, Bulking Time 10 seconds ~ 300 seconds.
3. a kind of natural ore according to claim 1 is the method that PVC stabilizer prepared by raw material, it is characterized in that: diluted acid described in second step is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the mass concentration of diluted acid is 1% ~ 15%; Heating temperature is 60 DEG C ~ 100 DEG C; Magneton rotating speed is 100 turns ~ 3000 turns, 10 minutes ~ 150 minutes time, and vacuum-drying temperature is 70 DEG C ~ 120 DEG C.
4. a kind of natural ore according to claim 1 is the method that PVC stabilizer prepared by raw material, it is characterized in that: the modified expanded vermiculite power of the 3rd step is broken to 160 order ~ 300 orders, diluted acid is formic acid, acetic acid, propionic acid, and mass concentration is 0.1% ~ 10%, 5 minutes ~ 120 minutes time.
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Cited By (5)
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CN106589451A (en) * | 2016-12-14 | 2017-04-26 | 塔里木大学 | Method for preparing PVC heat stabilizer by taking vermiculite as raw material |
CN106634943A (en) * | 2016-12-14 | 2017-05-10 | 塔里木大学 | Method of preparing thermochromic sensing material from vermiculite |
CN108975412A (en) * | 2018-07-28 | 2018-12-11 | 塔里木大学 | A method of iron compound is prepared from raw ore vermiculite |
CN114572966A (en) * | 2022-03-17 | 2022-06-03 | 无锡东恒新能源科技有限公司 | Method for synthesizing carbon nano tube based on layered structure iron-cobalt-aluminum catalyst |
CN115124042A (en) * | 2022-07-14 | 2022-09-30 | 塔里木大学 | Environment-friendly method for preparing high-surface-area layered silicon dioxide by vermiculite |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106589451A (en) * | 2016-12-14 | 2017-04-26 | 塔里木大学 | Method for preparing PVC heat stabilizer by taking vermiculite as raw material |
CN106634943A (en) * | 2016-12-14 | 2017-05-10 | 塔里木大学 | Method of preparing thermochromic sensing material from vermiculite |
CN106589451B (en) * | 2016-12-14 | 2018-04-06 | 塔里木大学 | A kind of method that PVC heat stabilizer is prepared using vermiculite as raw material |
CN106634943B (en) * | 2016-12-14 | 2019-07-23 | 塔里木大学 | A method of discoloration sensing material is prepared by raw material of vermiculite |
CN108975412A (en) * | 2018-07-28 | 2018-12-11 | 塔里木大学 | A method of iron compound is prepared from raw ore vermiculite |
CN114572966A (en) * | 2022-03-17 | 2022-06-03 | 无锡东恒新能源科技有限公司 | Method for synthesizing carbon nano tube based on layered structure iron-cobalt-aluminum catalyst |
CN114572966B (en) * | 2022-03-17 | 2024-01-09 | 无锡东恒新能源科技有限公司 | Method for synthesizing carbon nano tube based on layered structure iron-cobalt-aluminum catalyst |
CN115124042A (en) * | 2022-07-14 | 2022-09-30 | 塔里木大学 | Environment-friendly method for preparing high-surface-area layered silicon dioxide by vermiculite |
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